Process fob treating oils with sul



May 3, 1938. El 1 GOHR 1 2,115,847

PROCESS FOR TREATING 0114s WITH SULPHURIC ID AND FOR PREPARING IMPROVED WETTING AGENTS AND `JTERGENTS Filed NOV. 9, 1934 ITER Az/rALl /vLe-T ,$41.7- soLur/mv I ourber pfLu rs Ac'lo OUTLET* @mmf 24 I 2z if] @ffm .SETTL ING- DR UM ALcoHoL .SToRAc'E j TA VK Patented May 3, 1938 UNITED STAT-Es PATENT iol-*Flieg PROCESS Fon 4'rmm'rmci ons WITH SUL- PHURIC ACID AND Fon-PREPARING 1M- PROVED WETTING GENTS AGENTS ANDY DETER- Edwin. J. Gom, Elizabeth, N. J., assigner toV Standard Oil Development Company, a corpo` l ration oifDelaware' This invention. relates to anfimproved methodfor treating oils' with'strong sulphuric reagents and for the preparation of improved products therefrom and relates more particularly to the i5 treatment of hydrocarbon oils containing olefins awithv fuming 2 sulphuric acid for the preparation of improvedsulphuricderivatives which are useg ful as wetting agents and detergents.

.f In the treatment of olens and unsaturated hydrocarbon oils lsuch as acid-reactive crude oils and Ifractions thereof and cracked oils containing oleflns, with strong or fuming sulphuric acid, considerable oxidation and polymeriza- 4,tion ordinarily occurs with the formation of ob- H1-15-`;lectionable colorY bodies and resulting impair- Vment in the quality of kboth the oil and the sulphuric 'derivatives' obtained; These disadvantages are particularly noted when using fuming sulphuric acid as the treating agent.

` 'g 'so' It is an object of this invention to-provide an improved process by which the above disadvantagesare largely 'and in many instances even substantially'completely avoided `and by which improved products such as rened oil and sulphuric 'deriva-tives of high quality may be directly obtained. without the necessity of subsequent refining operations toremove undesirable byproducts of the acid treating process. These and further objects will be ascertained from the following descriptionfof lthe invention and the It .hasV been proposed to conduct the acid-oil reaction at such low temperatures that these objectionable side reactions are inappreciable. This,

' 35 however, requires considerable refrigeration due to the exothermic nature of the process.'

, It has now been discovered that this reaction, and the subsequent steps involved in the prepara- `tionand separation of the products, may be conu 40 ducted at higher temperatures than would otherwise be possible if the time of reaction is suitably shortened. The rate of reaction of fuming slphurlc; acid with olenes of more than about .eight carbon-atoms per molecule to form monor 'A 46 alkyl `sulphates, for example, has been observed to be substantially instantaneous. Theftimeof contactzrequired to complete the acid-oil reaction accordingly' depends largely upon the rapidity and'degree of intimacy obtainedy inthe mixing of the'- reagents. It is desirable that this mixing be as rapid and complete as possible and that the reaction mixture l,be thereafter immediately neutralized or dilutedto stop undesirablensiglereactions. .While higherY temperatures are permitted 555 if. theV reaction is conducted under such conditions, it is still necessary to remove the exother- I mic heat ofnreaction in order 'to prevent overheating. Suitable means' areV accordingly provided for cooling vthe reaction mixture, either directly or indirectly. Fork example, the reagents 5 may be contacted in a narrow. vstream viiowing at highvelocity over baiiles and confined between externally cooled walls, or the mixing may be accomplished in a vessel of small capacity, such as a turbo. mixer, and the vresulting mixture lo passed directly into a cooling coil. The mixing vessel may also be cooled. j 1^ The drawing presents ai diagrammatic illustration of one. suitable method for carrylngout this invention and illustrates the ilow of mate- 15 rials.

A strong sulphuric treating-reagent such as fuming sulphuric acidpis supplied by line I to a mixer 2`which may be of anydesired construction but is 'preferably arranged to provide for rapid and intimate admixture of the materials m supplied thereto. The mixer, for example, can be a homogenizer, a colloid mill,y etc. An acidreactive oil such as pure or mixedolens alone or in admixture with relativelyinert carrying vehicles such as hydrocarbon oils, carbon tetrachloride, methyl alcohol, etc., is supplied through line 3. Both acid and olefinic materials are supplied to the mixerat preferably a temperature not higher than the maximumreaction temperature desired and either mayy suitably be cooled 10 to40 degrees or more vbelow this temperature. The mixing vessel'may be supplied with cooling jackets, internal cooling coils or other means for removing the heat' of reaction. 'I'he 35 reaction mixture is preferably passed immediately through cooling coil 4 to remove Ythe heat formed, and to' yprevent; undue'rise in temperature. The period during which the reaction'mixture remains in the mixingvessel and in the cool- D lng coil is conveniently' considered as the time of contact of the reagents. y

The reaction isstopped abruptly nypassing the mixture from cooler 4 into a second mixing vessel 5 which maybe similar to mixer 2 and which may 5 also be provided with suitable cooling' means. wateigpreferably cooled tolas 10W a temperature as possible, is supplied to mixer -5 by line 6in sufcient amount to dilute the total free sulphuric acid andsulphuric anhydride to a iinai'sulphuric 50 lacid strength (based on total free acid and Water present) preferablyof about 40 to 60%. (Oi

course, if the reaction is conducted in the presence tetrachloride, dichlor and tetrachlor ethane, and the like, the amount of water added to dilute the sulphuric acid will be adjusted to cause separation of acid from the oil phase, and in the following and any unreacted organic material. In using a centrifuge for this separation, the speed of separation permits somewhat higher dilution and separation temperatures if the mixture is passed into the centrifuge as quickly as possible after dilution. At least a part of the dilution may be accomplished by the addition of cold water, with mixing, at the centrifuge inlet, and water may evenbe sprayed on the surface of the rotating mixture in the centrifuge, preferablyin the inlet zone of preliminary separation. It is then passed by line III into vmixer II in which itis contacted with a neutralizing agent, preferably an aqueous solution of an alkali such as sodium or potassium hydroxide or carbonate or ammonia which issupplied by line I2. If it is not desired to recover the excess acid, the total reaction mixture without' dilution may be passed by lines I3 and III directly into the mixer II and may be neutralized therein. The mixer II should also be provided with suitable cooling means or else the neutralized mixture shouldbe passed immediately into an after-cooler such as cooler I4. The reaction mixture, after dilution and/or neutralization to remove excess strong acid and to prevent the formation of undesirable by-products, may then be treated in any desired manner for the separation of residual cil, sulphuric derivatives, and organic matter. 'The means described herein for accomplishing this separation are merely illustrative as it is recognized that numerous other methods and modifications of the described method can be used in substitution therefor. A water soluble alcohol which is preferably of 90 to 95% vor higher concentration may be supplied by lines I5 and I0 as an aid in preventing the thickening of the mixture on neutralization and to aid in the subsequent separation of the neutralized products.

The neutralized mixture from mixer II passes into a second gravity separator I6 which may also be either a settling tank or a centrifuge. The nature and extent of the separation occurring in separator I6 is influenced by the amount and concentration of the alcohol present. If suflicient concentrated alcohol is added to give a resulting concentration of about 10 to 50% soap in the alcohol, three layers are formed, namely a lower or heavier layer of a saturated aqueous salt solution containing most of the sulphates, a middle alcoholic solution of the neutralized sulphuric derivatives or soaps, and an upper or lighter layer consisting of unreacted oil containing some soap and alcohol. 'I'he lower layer of aqueous salts is separately withdrawn by line Il. The middle layer of alcoholic soap solution is passed by line I8 into mixer I9 where it is mixed with sufficient additional concentratedalcohol to raise the alcohol concentration vvof the-mixture (based on total alcohol and water present) to above This causes the precipitation of substantially all the remaining inorganic salts which may be removed by suitable separation means 20 which may be either a lter and centrifuge or other suitable apparatus. The alcoholic solution of soap is then passed by lines 2| and 22 into still 23 from which most of the alcohol is removed as distillate by line 24. This alcohol distillate ls condensed in condenser 25 and passed to storage 26 from which it may be drawn for repeated use as already described. The distillation residue,v

consisting of a thick solution or slurry of the soaps in watervwhich may contain some undistilled alcohol, is passed by line 21 to a suitable drying means such as drum dryer 28. The soaps may also be dried in a spray dryer by atomization into a heated current of inert gases or air, or may be dried more slowly in cake form or in any other desired manner.

The upper oil layer from settler IG'may be passed byv line 29 into mixer 30 in which it is agitated with a 50% aqueous alcohol solution supplied by line 3I. The mixture then passes by line 32 into settling means 33 which may be either a tank or a centrifuge, in which an upper layer of oil separates from a lower aqueous alcohol layer containing substantially all the soaps and alcohol originally present inthe oil. The oil is withdrawn by line 34 and may be distilled yto recover traces of alcohol therefrom and may be subjected to any additional refining and fractionation steps considered desirable for the production of a'flnished oil. The lower or heavier aqueous alcohol solution is passed by lines 35'and 22 into the ystill 23.

If desired, as in the production of a crude commercial grade of soap containing inorganic salts, only sumcient alcohol may be added by line I5 to break the .emulsion formed on neutralization.

In this case only two layers form in separator I6namely, a lower aqueous alcoholic solution of soap and inorganic-salts and an upper oil layer containing aV small amount ofr soap and alcohol.

The upper layer maybe processed as described.

above and the lower layer may be passed directly into still 23 by lines I8, 36, 35 and 22, bypassing mixer I9 and filter 20.

The present invention may be applied generally in the refining of oils to substantially any oil containing acid reactive components such as petroleum oils and lubricating fractions thereof and more particularly cracked oils. It is of especial application in the preparation of high quality detergents and wetting agents which are insensitive to hard water, from oleflns of about 8 to 22 or more carbon atoms vper molecule, preferably having the carboni atoms connected in a straight chain and having the double bond at or near the end thereof. Organic compounds containing an oleflnic linkage, such as unsaturated fattyalcohols, for example, oleyl alcohol, and unsaturated fatty acids, such as oleic acid,.may also be treated according to the process of this invention. Detergents can also be `prepared according to the present invention from cracked paraillnic hydrocarbons and mixtures thereof such as parafiln wax and petrolatum, described in copending application, Serial No. 704,749, viled December 30, 1933, by William J. Sweeney. Wetting agents and detergents may be prepared by using the process of the present invention In treating cracked petroleum oils generally as de- Y 352,313, med

November 9, 1934, by Raphael R. Rosen. l Y

The use Aof the present inventionfor the prep- (arationiof high'quality detergents, is illustrated .in theV following example:

Example` y n f,- lff'raction boiunghetween 35o and 600 F.,

specific gravity 0.75, obtained by the destructive distillation -of parailin wax at a pressure of about Y 30vlbs. per square inch, is mixed with 13.5 volumes "'jfo'fy fuming sulphuric acid containing 20% by "weight of sulphuric anhydride per .100 volumes 4 vof cracked wax. A stream of the crackedwax A4is brought continuously into contact, with agi- Ytation, by.means of adriven propellordirected against bailles,y with a stream of the fuming acid.

`the lrate of supply'of the latter being so adjusted asto maintain at all times a slight excess'of sulphuric acid above that theoretically required :for the formation of mono-alkyl sulphates with the total olenes present. Cooling is supplied to -maintain a temperature of the reaction mixture of about 68 F. After a time of contact of 120 4seconds the mixture is diluted in a second mixing 'vessel with sufficient water to produce a dilute sulphuric'acid of about 60% strength, which is y Vvpermitted to separate as a separate layer and is withdrawn. A temperaturebelcw 80 F. is maintained throughout this dilution step and the subsequent separation. Fifty volumes of isopropyl alcohol are then added and the mixture is neutralized with an aqueous solution containing 15 `to 20% of sodium hydroxide with cooling to main- .,tain the temperature at about 80 to 120 F.

Three layers then are permitted to form on vstanding as described in the above description of the drawing. The middle layer of alcoholic soap solution is mixed with an equal Volume of isopropyl alcohol and is then filtered to separate out `ftheprecipitated inorganic salts. The alcoholic ltrate isthen reduced to dryness by evaporav.tion and nally on a drum dryer thereby'produc- 1 ing a yield of 40% (by weight of the oil treated) of a light colored salt-free soap of high detersive properties. A 0.2% solution of this soap in water i is. water-white in color and is a highly effective f laundering agent in both hard and soft water and in sea water.

An even shorter time of contact than that reaction to be completed in not more than 1 to v2 minutes. The reaction temperature also affects the extent of side reactions and the quality of the f products very materially and is inversely related to the time of contact in this effect. It is accordingly possible to operate at higher temperatures if v.the time of contact is made sufficiently short. For example, ordinary operations in which agitation is conducted for 30 minutes to an hour v` or longer in the preparation of detergents by treating cracked parafiin wax with fuming sull'phuric acid must be conducted at temperatures ,t .below about 30 F. in order to obtain a product of equal quality to that obtained with a reaction temperature of 68 F. in the above example.

1Somewhat yhigher temperatures may be used ywithout impairment in quality'if the time of reaction is further shortened below the 2 minutes used in this example. It' is generally undesirable to use reaction temperatures above about 100 F.

in the preparation of detergents'ofhigh quality products are desired and light coloris not essential, higher reaction temperatures of 125 to ,about 175 F. may be used. The timeof reaction 'in such cases is less than one minute and is preferably less than half a minute.

The use of a constant excess of acid'during the treating reaction is no part of the present invention, but is described more fully and claimed in copending application, Serial No. 752,312 filed November 9, 1934 by Fulton and Vesterdal. I1 the treating conditions are such that an excess of olenes is present, resulting in the presence of unstable dialkyl sulfates in the inal soap, the soap may be stabilized by limited hydrolysis or by boiling in the presence of dilute aqueous caustic soda, according to the process of copending application, Serial No. r422,838, led April 28, 1934, by Fulton and Vesterdal, or by the addition of buffers to the soap or its solution according to copending application Serial No. 752,287 filed November 9, 1934 by Hyym E. Buc. It is also desirable to add a slight excess of an alkali to solutions of such soaps before'drying the soaps, according to copending application Serial No. 704,790, le'd December 30, 1933, by Hans S. Vesterdal.

The strength of acid may be adjusted as desired and is preferably selected so as to obtain an acid which is liquid at the treating temperature used; for example, about 10 to 25% sulphuric anhydride. While fuming acids of about 5 up to about 65% content of sulphuric anhydride may be used, it is generally unnecessary to use the stronger acids because of thedesirability of maintaining at all times in the acid treating reaction an excess of sulphuric acid (HzSO4) above an equal molecular proportion of acidl to olen.

. 'Ihis invention is not to be limited to any specific description or examples which have been presented herein solely for purposes of illustration but is to be limited only bythe following claims in which it is desired to claim all novelty insofar as the prior art permits.

I claim:

1. Process for the production of improved detergents, comprising intimately mixing fuming sulphuric acid with an acid reactive essentially aliphatic hydrocarbon oil of more than 8 carbon atoms for a period less than one minute while maintaining the temperature Iin the range from 30 to 175 F., immediately diluting with water to provide acid strength below 60%.

2. Process for the production of improved detergents, comprising intimately mixing fuming sulphuric acid with an acid reactive essentially aliphatic hydrocarbon oil of more than 8 carbon atoms for a period less than five minutes while maintaining a temperature in the range from 30 to 100 F., immediately diluting with water to provide acid strength below 60%.

3. Process for the production of improved deterlents, comprising intimately mixing fuming sulphurc acid with an acid reactive essentially aliphatic hydrocarbon oil, boiling between 350 and 600 F., obtained by the destructive distillation of a paraflin wax, for a period of two minutes while maintaining the temperature of the reaction in the range from to 68 F., immediately diluting with water to provide acid strength below separating the sulphuric acid derivatives from the diluted acid, while maintaining a temperature below F. during the dilution and separation steps.

4. Process for the production of improved detergents, comprising yintimately mixing fuming sulphuric acid with an acid reactive essentially aliphatic petroleum oil of more than 8 carbon atoms for a period less than ten minutes while maintaining the temperature in the range of 30 to F., immediately diluting with Water to provide acid strength below 60%, 'separating the 7. Process in accordance with claim 1 in which the concentration of the excess sulphurio acid is reduced by neutralization.

`EDWIN J. GOHR. 

